Chlorination apparatus



Oct. 27, 1931. E. B. coNKLlN cHLoRINATIoN APPARATUS Original Filed Dec. 26

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INVENTOR EARL B/DDL A: Co/Vkl. 1^/

BY /SH-:m

ATTORNEYS Pamed. oct. `27, 1era naar. aromas comm, or armoires, maw Yonx,

'ro THE soLvAY rnocms conm, or soLva NEW YORK aseguraron.'Y BY :um assioma.

' cmaohma'non mamrus riginal application died Deoember'l8,1102$, Serial lo. 882,712. Divided and this application filed April 8, 1926. Serial Ilo. 99,545. y

This invention relates to apparatus adapted for the catalytic chlorination o f liqulds, and more particularly for the slde-cham chlorination of benzene derivatives or homo- 5 logues such as toluol.- A specific object of the invention is to provide means for .the production of benzyl chloride by an etliclent and continuous procedure.

Heretofore, as outlined in the patent of Gibbs and Geiger, No. 1,246,7' 39 of November 13, 1917, the then prevailing methods for the production of side-chain chlorine substitution products of toluol-benzyl and benzal chloride and benzotrichloride consisted either (a) of batch'or intermittent processes in which a given amount of toluol is treated in liquid form with chlorine gas until the `reaction had proceeded to a predetermined point or (b) of processes in which toluol as .gas was introduced into suitable apparatus in which it came in contact withgaseous chlorine. In the formerA or batchv process, .after the reaction had reached a predetermined point, the charge was removed and treated for the isolation of the desired product in a moreor less pure condition. Light or heat or a catalyst, alone orin combination, are used to favor the reaction. An example of a specic process operating along these lines is given in Patent No. 1,345,373 to Kyrides, July 6, 1920. Processes of this character have the disadvantage of fluctuating conditions and relatively large apparatus. Large apparatus is in this case a particular disadvantage on account of the highly intlammable nature of toluol and the necessity of using glass in order to obtain the advantage of illumination either by sunlight or some artificial source of light.

In the other type or process, in which t'oluol is chlorinated.while in gaseous form, it

`was necessary to employ a temperature above that of the boiling point of toluol 111 C.) and inI the reaction product unatt'acked toluol, which is .usually considerable in amount, requires to be separated andA 'returned to the system for further treatment. Light or a catalyst or .bothV are employed as accelerating agents. `Patent No. 1,202-

040, C. Ellis, october 24, 1916, 'aescribes accelerating agent therein.

such a process and the patent 'to Gibbs and Geigerl first referred to, No.'1,246,739, is for a modification of this second type of proce m YORK, A. CORPORATION Q1'. v

and for the use ofultraviolet rays as the Processes of this' character have the disadvantage of working with an :iniiammable material in vaporrform and are confronted with the difficulty of maintaining large apparatus at'an elevated` temperature and a constant 'temperature ysuch that condensationl does not take place.A The proce carried on in the new apparatus in contradistinction to the process of the prior art, is one in which the reaction proceeds continuously and in' the1 liquid phase. Uniform conditions are obtained and the output from a unit installation is relatively large. Other advantages will be evident from the detailed description.-

The new apparatus is illustrated in the accompanying drawings in which Fig. 1 is a s1de elevation of the apparatus. Fig. 2 is an enlarged sectional view of a detail and Fig.

3 is a horizontal section on line 3 3 of Fig. 2. In thesedrawings'A is a tower constructed of sections B of glass filled with suitable packing C such as glass Raschig rings.. The

glass sections are constituted of a material of the type known inthe market as pvrex glass, a transparent vitreous'material which is not destroyed by exposure to'heat. Each of the glass sections B o f the tower Aare approximately 6 inches in diameter and apf proximately 4 feet in length. A suitable cement D., resistant to chlorineand the Vother reaction substances. may be usedA in the connection between adjacent glass sections B and it is preferable to employ packing means like those shown in Figs. 2 and 3. Toluol.` preferably hot and in regulated amount., is conat the various pipe connections 'hereinafter I.'

referred to. although for the glass sections tinuously introduced into the top of the tower 4at E and dry,lpure chlorine gas at F at the bottom of the tower. If sunlightis not available, artificial illumination, such as that from electric or mercury lamps, may be usedby placing lamps G at-regular the tower A. The chlorinated and finished intervals around.-

product is continuously' withdrawn through the line H. The hydrochloric acid gas which is produced by the reaction between the toluol and the chlorine escapes thrfghthe line I and leaves the system through the line J and y may be utilized by absorption in water with cleats Q rest boards S each centrally apertured to support one o'f the glass sections B, preferably on a cushioning ring R. The annular space between adjacentsections B mayr be filled with cork rings T suitably treated, as by soaking in glue, said cork rings being surmounted by a lead follower ring U upon which rests a second plate' S similar to S in shape and positioned by the bolts V and nuts W. The bolt V passes loosely through S so that anv'de'sired tightening of the nuts W may be effected. The construction is preferablv such that the lower edge of each section B remains out of contact with the upper portion of the next lower section B.

The process as thus described consists essentially in passing'toluol as a liquid at a suitable temperature andv counter-current to a` current- 'of chlorine gas. downwardly 'through a tower transparent4 to light and which issubjected to sunlight or artificial illumination. With suitable regulation of the temperature and of the amount of toluol introduced through E and of the chlorine introduced through F the reaction proceeds rapidly and no recirculation of the exit liquor from H landfno cooling or heating of the tower is required in order 'to obtain lthe desired chlorination. Furthermore, practically complete utilization of the chlorine takes place so that very little, if any, chlorine escapes at J. Another result is that practically no chlorination in the benzene ring occurs with the production of `ring| chlorinated toluol yderivatives (chlor toluols) which impurities are difficult to remove. Thus an analysis of a crude benzyl chloride product made in accordance with the new process and having a specific gravity of 1.048 showed only a fraction of one percent. of ring chlorine and over sixteenpercent. side-chain chlorine.

' That corresponds to a benzyl chloride content of over fifty-seven percent. It rshould, however, be stated that the product to which Vthe foregoing analysis applies was a product of the process as'carried out in its early stages and that still more favorable analysismay be developed as the process is practiced on a commercial scale.

v is first started, the How of toluol at Lacasse luminated every 4 feet with two 200 watt electric lamps. A suitable temperature for the toluol introduced act E is 80 to 100 C. At the lower temperature the liquor returned throughLis very small. When theo ration is less than normal andthe flow is gradually increased during about -the first hour while the required] temperature and other chlonination conditions are becoming established throughout the tower. The operation then proceeds ractically automatically with a substantia ly constant and continuous introduction of toluol at E and a corresponding constant and continuous withdrawal of `crude product of the desired gravity at H. The capacity of the apparatus described is about 1800 lbs. of crude benzyl chloride product in twenty-four hours. The toluol may be conveniently supplied directlyi from a toluol still, the condenser of which is so adjusted as to cool the condensa-te to only 80 to 100 C. and with a small receiver or trap for the con densate provided with a constant level overiow so that the iiow through E is independent of the fluctuations in operation of the still.

The various gas and liquor lines'E, F, H, I, L, K and J are preferably made of glass or of lead.

The crude product from H may be treated in a variety of ways for the isolation of 'the chlorine derivative depending on the production of benzyl chloride but with proper adjustments it should be suitable for further chlorination of toluol to produce benzal chloride and benzotrichloride and for the production of side-chain chlorine substitution products of other side-chain aromatic hydrocarbons besides toluol.

The invention thus contemplates the treatment not only of toluol but of Iits homologues. It will be apparent that a glass tower feet or so in height and 6 inches or so in diameter and composed of a multiplicity of tubular glass units is a tower which is not self-supporting but requires support from the eXterior. In this art the use of a glass tower of this type is, so far as the applicant is aware, entirely novel. Other material than. glass may be used in the construction of such a tower provided it possesses the qualities of trans arency, durability and resistance to the chemicals to which it is exposed and the temperatures involved. Where in the claims eifectlve light rays are referred to, they are intended to include all those rays or emanations which favor halogenation whether such rays are luminous or invisible.

Numerous modifications in the detail of construction and operation may obviously be employed without departing from the spirit of this invention.

The present application is a division of an application filed by me on December 26, 1923, under Serial N o. 682,712.

I claim:

1. An apparatus for the catalytic chlorination of liquids which comprises a tower, external means for supporting it, the tower as a whole being of such great elongation as contrasted with its width as to be incapable of self-support, requiring the named external supporting means to maintain it in position, said tower being composed of a multiplicity of tubular sections composed of heat-resisting transparent glass, the sections being joined end to end by chlorine-resisting cement means for emitting rays adapted to catalyze the chlorination positioned adjacent to said transparent glass sections, said tower having an inlet for a liquid starting material at its upper end and an inlet for chlorine gas at its lower end and an outlet for product at its lower end, said tower containing filling material resistant to the chemicals traveling through the same and having also an outlet near its upper end for the gaseous products of the reaction.

2. An apparatus for the catalytic chlorination of liquids which comprises a tower, externalmeans for supporting it, the tower as a whole being of such great elongation as contrasted with its width as to be incapable of self-support, requiring the named external supporting means to maintain it in position, said tower being composed of a multiplicity of tubular sections composed of heat-resisting transparent glass, the sections being joined end to end by chlorine-resisting cement means for emitting rays adapted to catalyze the chlorination positioned adjacent to sald transparent glass sections, said tower having an inlet for a liquid starting material at its upper end and an inlet for chlorine gas -at its lower end and an outlet for product at its lower end, said tower containing filling material resistant to the chemicals traveling through the same and having also an outlet near its upper end for the gaseous products of the reaction, a gas line connectmg the upper outlet with means for collect.

ing hydrochloric acid, a condenser for starting material in saidv line and return flow pipe from said condenser to said tower.

3. An apparatus for the catalytic chlorination of liquids which comprises a tower, external means for supporting it, the tower as a whole being of such great elongation as contrasted with its width as to be incapable of self-support, requiring the named external supporting-means to maintain it in position, sa1d tower being composed of a multiplicity of tubular sections composed of heat-resisting transparent glass, the sections being joined end to end by chlorine-resisting cement, means for causing light rays to become effective through said glass sections upon the material passing through the tower, said tower having an inlet for a liquid starting material at its upper end and an inlet for chlorine gas at its lower end and an outlet for product at its lower end,said tower containing filling material resistant to the chemicals traveling through the same and having also an outlet near its upper end for the gaseous products of the reaction.

4. An apparatus for the catalytic chlorination of liquids which comprises a tower, eX- ternal means for supporting it, the tower as a whole being of such great elongation as contrasted with its width as to be incapable of self-support, requiring the named external supporting means to maintain it in position, said tower being composed of a multiplicity of tubular sections composed of heat-resisting transparent glass, the sections being joined end to end by chlorine-resisting cement` means for causing light rays to become effective through said glass sections upon the material passing through the tower, said tower having an inlet for a liquid starting material at its upper end and an inlet for chlorine gas at its lower end and an outlet for product at its lower end, said tower containing filling material resistance to the chemicals traveling through the same and having also an outlet near its upper end for the gaseous products of the reaction, a gas line connectingr the upper outlet with means for collecting hydrochloric acid, a condenser for starting material in said line and a return flow pipe from said condenser to said tower.

In testimony whereof I have hereunto set my hand.

EARL BIDDLE CONKLIN. 

